U.S. patent number 6,475,568 [Application Number 09/854,583] was granted by the patent office on 2002-11-05 for block, non-(ab)n silicone polyalkyleneoxide copolymers with tertiary amino links.
This patent grant is currently assigned to Crompton Corporation. Invention is credited to Anna Maria Czech.
United States Patent |
6,475,568 |
Czech |
November 5, 2002 |
Block, non-(AB)n silicone polyalkyleneoxide copolymers with
tertiary amino links
Abstract
A composition is disclosed that comprises non-hydrolyzable,
block, non-(AB).sub.n type copolymers comprising units of the
formula {XR.sup.2 [(SiO(R.sup.1).sub.2 ].sub.x Si(R.sup.1).sub.2
R.sup.2 X}, units of the formula {YO(C.sub.a H.sub.2a O).sub.b Y},
and linking groups --NR.sup.3 --, wherein R.sup.1 is alkyl, R.sup.2
is a divalent organic moiety, X and Y are independently selected
divalent organic groups formed by the ring opening of an epoxide,
R.sup.3 is selected from the group consisting of alkyl, aryl,
aralkyl, oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl, a=2 to 4, b=2 to 100, and x=1 to
500.
Inventors: |
Czech; Anna Maria (Cortlandt
Manor, NY) |
Assignee: |
Crompton Corporation
(Middlebury, CT)
|
Family
ID: |
25319090 |
Appl.
No.: |
09/854,583 |
Filed: |
May 15, 2001 |
Current U.S.
Class: |
427/386;
424/70.12; 8/128.3; 8/127.5; 556/445; 556/444; 528/28; 427/389;
427/389.9; 427/387; 528/27 |
Current CPC
Class: |
D06M
15/6436 (20130101); C08G 59/306 (20130101); D06M
15/647 (20130101); D06M 15/643 (20130101); A61Q
5/02 (20130101); A61Q 5/12 (20130101); C08G
77/46 (20130101); D06M 15/53 (20130101); A61K
8/90 (20130101); D06M 2200/50 (20130101); D06M
2200/00 (20130101) |
Current International
Class: |
A61Q
5/00 (20060101); A61Q 5/02 (20060101); A61Q
19/00 (20060101); C08G 77/46 (20060101); A61K
8/72 (20060101); D06M 15/53 (20060101); D06M
15/643 (20060101); A61K 8/90 (20060101); D06M
15/647 (20060101); D06M 15/37 (20060101); C08G
77/00 (20060101); B05D 007/00 () |
Field of
Search: |
;556/444,445 ;528/28,27
;8/128.3,127.5 ;424/70.12 ;427/389.9,389,386,387 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
19817776 |
|
Apr 1998 |
|
DE |
|
1213779 |
|
Nov 1970 |
|
GB |
|
Primary Examiner: Dawson; Robert
Assistant Examiner: Peng; Kuo-Liang
Attorney, Agent or Firm: Dilworth; Michael P.
Claims
What is claimed is:
1. A composition comprising non-hydrolyzable, block, non-(AB).sub.n
type copolymers comprising units of the formula {XR.sup.2
[(SiO(R.sup.1).sub.2 ].sub.x Si(R.sup.1).sub.2 R.sup.2 X}, units of
the formula {YO(C.sub.a H.sub.2a O).sub.b Y}, and linking groups
--NR.sup.3 --, wherein R.sup.1 is alkyl, R.sup.2 is a divalent
organic moiety, X and Y are independently selected divalent organic
groups formed by the ring opening of an epoxide, R.sup.3 is
selected from the group consisting of alkyl, aryl, aralkyl,
oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl, a=2 to 4, b=2 to 100, and x=1 to
500.
2. The composition of claim 1 wherein R.sup.1 is an alkyl group
having from one to four carbon atoms.
3. The composition of claim 1 wherein R.sup.2 is a divalent
hydrocarbon group comprising at least one carbon atom.
4. The composition of claim 3 wherein R.sup.2 further comprises at
least one hydroxy substituent thereon, at least one ether linkage,
or a combination of at least one hydroxy substituent and at least
one ether linkage.
5. The composition of claim 1 wherein the copolymers are end-capped
with secondary amino groups --NHR.sup.3 or tertiary amino groups
--NR.sup.3 R.sup.4, wherein R.sup.3 and R.sup.4 are independently
selected from the group consisting of alkyl, aryl, aralkyl,
oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl.
6. The composition of claim 1 wherein X and Y and independently
selected from the group consisting of --CH.sub.2
CH(OH)(CH.sub.2).sub.v CH(OH)CH.sub.2 --, --CH[CH.sub.2
OH](CH.sub.2).sub.v CH[CH.sub.2 OH]--, --CH.sub.2
CH(OH)(CH.sub.2).sub.v CH[CH.sub.2 OH]--, --(CH.sub.2).sub.v
--OCH.sub.2 CH(OH)CH.sub.2 --, and --(CH.sub.2).sub.v OCH.sub.2
CH(CH.sub.2 [OH])-- wherein v=2 to 6.
7. The composition of claim 1 wherein the ring-opened epoxides are
independently derived from members selected from the group
consisting of: .omega.(3,4-epoxycyclohexyl)alkylene,
.beta.-(3,4-epoxycyclohexyl)ethylene,
.beta.-(3,4-epoxycyclohexyl)-.beta.-methylethylene, and
.beta.-(3,4-epoxy-4-methylcyclohexyl)-.beta.-methylethylene.
8. The composition of claim 1 wherein the polyoxyalkylene blocks
represented by (C.sub.a H.sub.2a O) are made up of ethylene oxide
(a=2), propylene oxide (a=3), and butylene oxide (a=4) in a random
or blocked fashion.
9. The composition of claim 1 wherein the amine groups are
protonated or quaternized.
10. A method of making non-hydrolyzable, block, non-(AB).sub.n type
copolymers comprising units of the formula {XR.sup.2
[(SiO(R.sup.1).sub.2 ].sub.x Si(R.sup.1).sub.2 R.sup.2 X}, units of
the formula {YO(C.sub.a H.sub.2a O).sub.b Y}, and linking groups
--NR.sup.3 --, wherein R.sup.1 is alkyl, R.sup.2 is a divalent
organic moiety, X and Y are independently selected divalent organic
groups formed by the ring opening of an epoxide, R.sup.3 is
selected from the group consisting of alkyl, aryl, aralkyl,
oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl, a=2 to 4, b=2 to 100, and x=1 to 500,
wherein the method comprises reacting (1) polysiloxanes of the
formula QR.sup.2 [(SiO(R.sup.1).sub.2 ].sub.c Si(R.sup.1).sub.2
R.sup.2 Q, and (2) polyalkyleneoxides of the formula {ZO(C.sub.b
H.sub.2b O).sub.d Z}, wherein Q and Z are epoxide containing
groups, with at least one primary amine or a combination of primary
and secondary amines.
11. The method of claim 10 wherein R.sup.1 is an alkyl group having
from one to four carbon atoms.
12. The method of claim 10 wherein R.sup.2 is a divalent
hydrocarbon group comprising at least one carbon atom.
13. The method of claim 12 wherein R.sup.2 further comprises at
least one hydroxy substituent thereon, at least one ether linkage,
or a combination of at least one hydroxy substituent and at least
one ether linkage.
14. The method of claim 10 wherein the copolymers are end-capped
with secondary amino groups --NHR.sup.3 or tertiary amino groups
--NR.sup.3 R.sup.4, wherein R.sup.3 and R.sup.4 are independently
selected from the group consisting of alkyl, aryl, aralkyl,
oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl.
15. The method of claim 10 wherein X and Y and independently
selected from the group consisting of --CH.sub.2
CH(OH)(CH.sub.2).sub.v CH(OH)CH.sub.2 --, --CH[CH.sub.2
OH](CH.sub.2).sub.v CH[CH.sub.2 OH]--, --CH.sub.2
CH(OH)(CH.sub.2).sub.v CH[CH.sub.2 OH]--, --(CH.sub.2).sub.v
--OCH.sub.2 CH(OH)CH.sub.2 --; and --(CH.sub.2).sub.v OCH.sub.2
CH(CH.sub.2 [OH])-- wherein v=2 to 6.
16. The method of claim 10 wherein the ring-opened epoxides are
independently derived from members selected from the group
consisting of: .omega.-(3,4-epoxycyclohexyl)alkylene,
.beta.-(3,4-epoxycyclohexyl)ethylene,
.beta.-(3,4-epoxycyclohexyl)-.beta.-methylethylene, and
.beta.-(3,4-epoxy-4-methylcyclohexyl)-.beta.-methylethylene.
17. The method of claim 10 wherein the the polyoxyalkylene blocks
represented by (C.sub.a H.sub.2a O) are made up of ethylene oxide
(a=2), propylene oxide (a=3), and butylene oxide (a=4) in a random
or blocked fashion.
18. The method of claim 10 wherein the amine groups are protonated
or quaternized.
19. A method for softening a substrate comprising applying to said
substrate a composition comprising non-hydrolyzable, block,
non-(AB).sub.n type copolymers comprising units of the formula
{XR.sup.2 [(SiO(R.sup.1).sub.2 ].sub.x Si(R.sup.1).sub.2 R.sup.2
X}, units of the formula {YO(C.sub.a H.sub.2a O).sub.b Y}, and
linking groups --NR.sup.3 --, wherein R.sup.1 is alkyl, R.sup.2 is
a divalent organic moiety, X and Y are independently selected
divalent organic groups formed by the ring opening of an epoxide,
R.sup.3 is selected from the group consisting of alkyl, aryl,
aralkyl, oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl, a=2 to 4, b=2 to 100, and x=1 to
500.
20. The method of claim 19 wherein R.sup.1 is an alkyl group having
from one to four carbon atoms.
21. The method of claim 19 wherein R.sup.2 is a divalent
hydrocarbon group comprising at least one carbon atom.
22. The method of claim 21 wherein R.sup.2 further comprises at
least one hydroxy substituent thereon, at least one ether linkage,
or a combination of at least one hydroxy substituent and at least
one ether linkage.
23. The method of claim 19 wherein the copolymers are end-capped
with secondary amino groups --NHR.sup.3 or tertiary amino groups
--NR.sup.3 R.sup.4, wherein R.sup.3 and R.sup.4 are independently
selected from the group consisting of alkyl, aryl, aralkyl,
oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl.
24. The method of claim 19 wherein X and Y and independently
selected from the group consisting of --CH.sub.2
CH(OH)(CH.sub.2).sub.v CH(OH)CH.sub.2 --, --CH[CH.sub.2
OH](CH.sub.2).sub.v CH[CH.sub.2 OH]--, --CH.sub.2
CH(OH)(CH.sub.2).sub.v CH[CH.sub.2 OH]--, --(CH.sub.2).sub.v
--OCH.sub.2 CH(OH)CH.sub.2 --; and --(CH2).sub.v OCH.sub.2
CH(CH.sub.2 [OH])-- wherein v=2 to 6.
25. The method of claim 19 wherein the ring-opened epoxides are
independently derived from members selected from the group
consisting of: .omega.-(3,4-epoxycyclohexyl)alkylene,
.beta.-(3,4-epoxycyclohexyl)ethylene,
.beta.-(3,4-epoxycyclohexyl)-.beta.-methylethylene, and
.beta.-(3,4-epoxy-4-methylcyclohexyl)-.beta.-methylethylene.
26. The method of claim 19 wherein the the polyoxyalkylene blocks
represented by (C.sub.a H.sub.2a O) are made up of ethylene oxide
(a=2), propylene oxide (a=3), and butylene oxide (a=4) in a random
or blocked fashion.
27. The method of claim 19 wherein the amine groups are protonated
or quaternized.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel block, non-(AB).sub.n,
linear copolymers comprising units of polysiloxane and
polyalkyleneoxide linked by tertiary amino groups, a method for the
preparation of these copolymers, and to the use of these copolymers
as conditioning ingredients in hair care and skin care products and
as textile softeners, particularly, re-wettable textile
softeners.
2. Description of Related Art
Examples of non-hydrolyzable siloxane-polyalkyleneoxide block
copolymers are known in the prior art.
U.S. Pat. No. 3,761,444 discloses an improvement in the manufacture
of epoxy substituted siloxanes. Lower molecular weight epoxy
substituted siloxanes are equilibrated with other siloxanes to
produce siloxane copolymers containing the substituents of both the
epoxy siloxane and the other siloxanes. This is accomplished with a
basic equilibration catalyst and in the presence of small
quantities of water and silanol.
U.S. Pat. No. 4,101,272 discloses a process for the treatment of
fibrous materials to improve their properties, in which the fibrous
materials are treated with a composition containing: a component A
selected from the class consisting of polyorganosiloxanes of the
general formula
in which n has an average value in the range 1.8 to 2.2, and R
represents organic radicals attached to the silicon atoms by
carbon-silicon bonds; wherein between 1.0 and 50 percent of the
radicals R consist of one or more organic radicals containing an
epoxide group and selected from the class consisting of:
1,2-epoxyethyl; 3,4-epoxycyclohexyl; 6-methyl-3,4-epoxycyclohexyl;
3,4-epoxycyclohexyl- 1-ethyl; 9,10-epoxystearyl;
3-(2,3-epoxypropoxy)propyl; p-(2,3-epoxybutyl)-phenyl; and
3-(3,4-epoxybutyl)cyclohexyl, and the remainder of the radicals R
consist of one or more organic radicals selected from the class
consisting of alkyl and aryl radicals; and a polyamine component B
which consists of one or more organic compounds each with two or
more primary and/or secondary amino groups attached to aliphatic
carbon atoms such that there are at least 5 carbon atoms per amino
group, or two or more groups capable of providing, by reaction,
primary and/or secondary amino groups; and allowing the components
A and B to react chemically.
U.S. Pat. No. 4,242,466 discloses organic ethers including
polyethers having two CH.sub.2 =C(R)CH.sub.2 -- end groups per
molecule wherein R is a monovalent hydrocarbon group that are
reacted with organohydrosiloxanes under hydrosilation reaction
conditions in the presence of a platinum catalyst to form
nonhydrolyzable siloxane block copolymers. Non-hydrolyzable linear
block copolymers substantially free of silicon-bonded hydrogen are
obtained with linear dihydropolyorganosiloxane reactants and linear
ethers or polyethers.
U.S. Pat. No. 4,833,225 discloses polyquaternary polysiloxane
polymers having defined repeating units. The compounds may be
synthesized by an addition reaction between an
.alpha.,.omega.-hydrogenpolysiloxane of a given formula and
epoxides which have a terminal olefinic bond, and reacting the
product obtained with a diamine. The polymers may be used in
cosmetic preparations, especially in hair cosmetics.
U.S. Pat. Nos. 5,807,956 and 5,981,681 disclose non-hydrolyzable,
block, (AB).sub.n A type, copolymers comprising alternating units
of polysiloxane and amino-polyalkyleneoxide and provide a method
for the preparation of these copolymers. Also provided is the use
of these copolymers as softeners, in particular durable,
hydrophilic textile softeners, which improve tactile properties of
the textiles substrates treated with the commercial soil release
finishes, without substantially detracting from their properties.
The copolymers have alternating units of polysiloxane [X(C.sub.a
H.sub.2a O).sub.b R.sup.2 [(SiO(R.sup.1).sub.2 ].sub.c
Si(R.sup.1).sub.2 R.sup.2 (C.sub.a H.sub.2a O).sub.b X] and
polyalkyleneoxides [YO(C.sub.a H.sub.2a O).sub.d Y] wherein R.sup.1
is a C.sub.1 to C.sub.4 alkyl, preferably methyl, R.sup.2 is a
divalent organic moiety, X and Y are divalent organic groups
selected from a secondary or tertiary amine and a ring opened
epoxide, such that when X is a ring opened epoxide, Y is an amine
and vice versa, a=2 to 4, preferably 2 to 3, b=0 to 100, d=0 to
100, b+d=1 to 100, preferably 10 to 50, and c=1 to 500, preferably
10 to 100.
U.K. Patent No. 1,213,779 discloses a process for the production of
an organo-silicon compound by the addition of a hydrogen-silane or
-siloxane to an olefinically-unsaturated organic compound in the
presence of a catalyst, trimethyl-dipyridine-platinum-iodide.
DE 19817776 A1 provides another example of the (AB).sub.n
aminopolysiloxane polyalkylyneoxide copolymers. These copolymers
are derived from reaction of the acrylate terminated polyether with
amine terminated polysiloxanes under Michael's addition
conditions.
The disclosures of the foregoing are incorporated herein by
reference in their entirety.
SUMMARY OF THE INVENTION
The present invention is directed to non-hydrolyzable, block,
non-(AB).sub.n type copolymers comprising units of
polydimethylsiloxane and polyalkyleneoxide linked by tertiary amino
groups.
In another aspect, the present invention is directed to a method
for the preparation of these copolymers from the epoxy terminated
polydimethylsiloxanes and epoxy terminated polyalkyleneoxides with
primary amines or a combination of primary and secondary amines,
where secondary amine functions as a chain stopper.
In still another aspect, the present invention is directed to the
use of these copolymers as conditioning ingredients for hair care
and skin care, as well as textile softeners to improve wettability
and tactile properties of textile substrates.
More particularly, the present invention is directed to a
composition comprising non-hydrolyzable, block, non-(AB).sub.n type
copolymers comprising units of the formula {XR.sup.2
[(SiO(R.sup.1).sub.2 ].sub.x Si(R.sup.1).sub.2 R.sup.2 X}, units of
the formula {YO(C.sub.a H.sub.2a O).sub.b Y}, and linking groups
--NR.sup.3 --, wherein R.sup.1 is alkyl, R.sup.2 is a divalent
organic moiety, X and Y are independently selected divalent organic
groups formed by the ring opening of an epoxide, R.sup.3 is
selected from the group consisting of alkyl, aryl, aralkyl,
oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl, a=2 to 4, b=2 to 100, and x=1 to
500.
In another embodiment, the present invention is directed to a
method of making non-hydrolyzable, block, non-(AB).sub.n type
copolymers comprising units of the formula {XR.sup.2
[(SiO(R.sup.1).sub.2 ].sub.x Si(R.sup.1).sub.2 R.sup.2 X}, units of
the formula {YO(C.sub.a H.sub.2a O).sub.b Y}, and linking groups
--NR.sup.3 --, wherein R.sup.1 is alkyl, R.sup.2 is a divalent
organic moiety, X and Y are independently selected divalent organic
groups formed by the ring opening of an epoxide, R.sup.3 is
selected from the group consisting of alkyl, aryl, aralkyl,
oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl, a=2 to 4, b=2 to 100, and x=1 to 500,
wherein the method comprises reacting (1) polysiloxanes of the
formula QR.sup.2 [(SiO(R.sup.1).sub.2 ].sub.c Si(R.sup.1).sub.2
R.sup.2 Q, and (2) polyalkyleneoxides of the formula {ZO(C.sub.b
H.sub.2b O).sub.d Z}, wherein Q and Z are epoxide containing
groups, with at least one primary amine or a combination of primary
and secondary amines.
In still another embodiment, the present invention is directed to a
method for softening a substrate comprising applying to said
substrate a composition comprising non-hydrolyzable, block,
non-(AB).sub.n type copolymers comprising units of the formula
{XR.sup.2 [(SiO(R.sup.1).sub.2 ].sub.x Si(R.sup.1).sub.2 R.sup.2
X}, units of the formula {YO(C.sub.a H.sub.2a O).sub.b Y}, and
linking groups --NR.sup.3 --, wherein R.sup.1 is alkyl, R.sup.2 is
a divalent organic moiety, X and Y are independently selected
divalent organic groups formed by the ring opening of an epoxide,
R.sup.3 is selected from the group consisting of alkyl, aryl,
aralkyl, oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl, a=2 to 4, b=2 to 100, and x=1 to
500.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A. Copolymer Structure
The block copolymers of the present invention have in their
structure polysiloxane units {XR.sup.2 [(SiO(R.sup.1).sub.2 ].sub.x
Si(R.sup.1).sub.2 R.sup.2 X}, polyalkyleneoxide units {YO(C.sub.a
H.sub.2a O).sub.b Y} and linking groups --NR.sup.3 --, wherein
R.sup.1 is alkyl, R.sup.2 is a divalent organic moiety, X and Y are
divalent organic groups formed by the ring opening of an epoxide,
R.sup.3 is selected from the group consisting of alkyl, aryl,
aralkyl, oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl, a=2 to 4, b=2 to 100, preferably 3 to
50, x=1 to 500, preferably 150.
R.sup.1 is preferably lower alkyl, e.g., an alkyl having from one
to four carbon atoms, i.e., methyl, ethyl, propyl, butyl, and
isomers of the foregoing, e.g., isopropyl, t-butyl, and the like.
More preferably, R.sup.1 is methyl.
R.sup.2 is preferably a divalent hydrocarbon group with at least
one carbon, which may have hydroxy substitutions thereon and/or
include an ether linkage. Preferably, it contains less than ten
carbon atoms. Within a particular molecule, each R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 may be the same or different.
The copolymers are preferably end-capped with secondary amino
groups --NHR.sup.3 or tertiary groups --NR.sup.3 R.sup.4, where
R.sup.4 is also chosen from the group consisting of alkyl, aryl,
aralkyl, oxygen-containing alkyl, oxygen-containing aryl, and
oxygen-containing aralkyl, and where R.sup.3 and R.sup.4 can be the
same or different.
The moieties comprising R.sup.3 and R.sup.4 preferably comprise
from one to about twenty carbon atoms, e.g., methyl, ethyl, propyl,
butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl, nonadecyl, eicosyl, methoxy, ethoxy, propoxy, butoxy,
phenyl, biphenyl, naphthyl, tolyl, xylyl, anthracyl, methoxyphenyl,
isomers of the foregoing, and the like.
The copolymers are not (AB).sub.n type because blocks may consist
of more than one unit, therefore the nominal length of the blocks
will vary. Moreover, blocks comprising more than one unit will be
interrupted with the amino groups. The number of units per molecule
is limited by the ability to handle high viscosity material, since
the viscosity is directly proportional to the number of units, but
practically there should be at least two of each unit and may be up
to 1,000 units. It is preferred that the terminal groups of the
copolymer be amino groups, as noted above.
The molecular weight of the copolymers can be modified by varying
the molar ratio of the epoxy component to amino component, by
varying the number of oxyalkylene units and the number of siloxy
groups within the polysiloxane blocks.
The ring-opened epoxides, represented by either X or Y, may be
aliphatic, cycloaliphatic, and may contain aromatic rings. They
also contain hydroxy groups and may contain an ether linkage.
Preferably, the ring-opened epoxide is chosen from the following:
--CH.sub.2 CH(OH)(CH.sub.2).sub.v CH(OH)CH.sub.2 --, --CH[CH.sub.2
OH](CH.sub.2).sub.v CH[CH.sub.2 OH]--, --CH.sub.2
CH(OH)(CH.sub.2).sub.v CH[CH.sub.2 OH]--, --(CH.sub.2).sub.v
--OCH.sub.2 CH(OH)CH.sub.2 --; --(CH.sub.2).sub.v OCH.sub.2
CH(CH.sub.2 [OH])-- with v=2 to 6. Alternatively, the ring-opened
epoxides may be derived from the following epoxycyclohexyl alkylene
groups, .omega.-(3,4-epoxycyclohexyl)alkylene,
.beta.-(3,4-epoxycyclohexyl)ethylene,
.beta.-(3,4-epoxycyclohexyl)-.beta.-methylethylene, and
.beta.-(3,4-epoxy-4-methylcyclohexyl)-.beta.-methylethylene.
The polyoxyalkylene blocks represented by (C.sub.a H.sub.2a O) or
(OC.sub.a H.sub.2a) may be made up of ethylene oxide (a=2),
propylene oxide (a=3), and butylene oxide (a=4) in a random or
blocked fashion. The ratio among such oxides is not of particular
importance, but may be adjusted as required for the desired
solubility parameters of the resulting copolymer.
B. Method of Manufacture
The compounds of the present invention are prepared by reacting two
species: (1) polysiloxanes QR.sup.2 [(SiO(R.sup.1).sub.2 ].sub.c
Si(R.sup.1).sub.2 R.sup.2 Q, and (2) polyalkyleneoxides [ZO(C.sub.b
H.sub.2b O).sub.d Z], which are the same as the formulae above
except that Q and Z are epoxide containing groups, with a primary
amine or a combination of primary and secondary amines, where the
secondary amine will function as a chain stopper. These species may
be manufactured by means known in the art or are commercially
available.
In an exemplary process, .alpha.,.omega.-hydrogenpolysiloxanes of
the general formula H(SiO(R.sup.1).sub.2).sub.x Si(R.sup.1).sub.2 H
are reacted in a first step with the unsaturated epoxides with a
terminal olefinic bond, such as allyl glycidyl ether, in the
presence of a hydrosilation catalyst, such as hexachloroplatinic
acid, at elevated temperature, to produce epoxy end-blocked
polysiloxanes. Such procedures are known in the art as indicated in
U.S. Pat. No. 3,761,444 and U.K. Patent No. 1,213,779. The
following are examples of suitable epoxides with terminal olefinic
groups. ##STR1##
In a second step, the epoxy end-blocked polysiloxanes and epoxy
end-blocked polyalkyleneoxides are reacted with primary amino
groups or a combination of primary and secondary amino groups.
Suitable epoxy end-blocked polyalkyleneoxides are represented, for
example, by DER 732 and DER 736 available from Dow Chemical Co. The
primary amines may, for example, be selected from ethylamine,
propylamine, butylamine, isobutylamine, hexylamine,
cyclohexylamine, benzylamine, ethanolamine, propanolamine, and the
like, the secondary amines may be selected, for example, from
diethylamine, dipropylamine, dibutylamine, diisobutylamine,
dihexylamine, dicyclohexylamine, dibenzylamine, diethanolamine,
dipropanolamine, and the like. The reaction is carried out in a
suitable solvent, such as an alcohol or a mixture of alcohol and
water at reflux. If the boiling point of the amine is lower than
the boiling point of the solvent, the reaction is conducted in a
pressurized vessel. Typically, the epoxy end-blocked polysiloxanes
and epoxy end-blocked polyalkyleneoxides are added to the solution
of the amine in the reaction solvent.
For practical purposes, the reaction is carried out with about a 1
to to about 30 percent, preferably about 1 to about 20 percent,
excess of the amine-containing species. Despite using an excess of
the amine used during the preparation of the copolymers whereby the
majority of the end-groups can be expected to be amines, it is
possible that the epoxy end group on the polysiloxane can undergo
side reactions with the solvent, water, or alcohol to form the
corresponding diol or ether alcohol.
After the reaction, the solution of the copolymer can be
neutralized by a direct addition of a Bronsted acid, such as acetic
acid, citric acid, tartaric acid, or fatty acids, such as stearic
or isostearic acid, to form an ammonium salt and the product is
isolated by distilling off the solvent at atmospheric or reduced
pressure. Depending upon the molecular weight and ethylene oxide
content of the copolymer, it may be a viscous oil or a wax.
It is also possible to isolate un-neutralized copolymer and then
proceed with neutralization (as described above) or quaternization
of the amino groups. Quaternization reaction of the amines
typically involves common alkylating agents, such as alkyl halides
or sulfates, and the resulting quaternium salts may offer improved
deposition properties or static electicity control as compared to
the starting amines or their salts.
An alternative way to produce quaternized structures is to react
the epoxy end-blocked polysiloxanes and epoxy end-blocked
polyalkyleneoxides with secondary amines selected, for example,
from diethylamine, dipropylamine, dibutylamine, diisobutylamine,
dihexylamine, dicyclohexylamine, dibenzylamine, dipropanolamine,
and the like in the presence of a stoichiometric amount of a
Bronsted acid, such as hydrochloric acid, sulfuric acid or acetic
acid. The reaction is carried out in a suitable solvent, such as an
alcohol or a mixture of alcohol and water at reflux.
C. Copolymer Uses
The copolymers of the present invention are primarily intended as
softeners for substrates, especially hair, fibers, and textiles.
While these copolymers can be used neat, for ease of application,
they are usually applied to the substrates dissolved, dispersed, or
emulsified in a suitable liquid medium. Preferably, they are
applied to the substrate from an aqueous solution, emulsion, or
suspension. They may also be applied as a solution in a non-aqueous
solvent, such as isopropanol, or in a liquid in which the copolymer
is miscible. More preferably, the copolymer is applied to the
substrate as an aqueous dispersion.
Aqueous emulsions of the copolymers can be prepared by combining
the copolymer with one or more emulsifiers, such as nonionic
surfactants, and diluted with water to a desired concentration.
Nonionic surfactants commonly employed in such emulsions can
include, for example, TERGITOL surfactants, available from Union
Carbide Chemicals and Plastics Co., Inc.
Stable aqueous dispersions of the copolymers can, for example, be
prepared by directly blending or mixing a solution of the copolymer
in a water miscible solvent, such as isopropanol, propylene glycol,
dipropylene glycol, or dipropylene glycol methyl ether, with water
to obtain the desired copolymer level.
Once prepared, the dispersions, emulsions, or solutions can be
applied to a substrate by any conventional means, such as by
spraying, dipping, kiss roll application, or other application
method typically employed in fiber, hair, or textile treatment. The
substrates that can be treated with the copolymers of the present
invention are exemplified by natural fibers, such as hair, cotton,
silk, flax, cellulose, paper (including tissue paper), and wool;
synthetic fibers, such as polyester, polyamide, polyacrylonitrile,
polyethylene, polypropylene, and polyurethane; and inorganic
fibers, such as glass or carbon fibers. Fabric substrates that can
be treated with the copolymers of the present invention are
exemplified by fabrics produced from the above-mentioned fibrous
materials or blends thereof.
In general, the dispersions, emulsions, or solutions are applied to
hair, fiber, or textile substrates such that up to 5 percent,
preferably 0.25 to 2.5 percent of the copolymer by weight of the
dry substrate remains on the substrate. Optionally, other additives
commonly used to treat hair or textile substrates can be employed
along with the copolymers of the present invention, including but
not limited to, additional surfactants, deposition polymers,
quaternary conditioning agents, curing resins, preservatives, dyes,
colorants, formularies, and the like.
Moreover, compositions comprising the copolymers of the present
invention can be used in personal care formulations, including
cleansers, body washes, soaps, lotions, creams, shaving cream, hair
sprays, conditioners, shampoos, deodorants, moisturizers,
sunblocks, and the like.
The copolymers of the present invention can be formulated into
these and other products together with one or more anionic
surfactants, one or more amphoteric surfactants, one or more
nonionic surfactants, and/or one or more deposition polymers or
thickeners.
Suitable anionic surfactants include sulfonated and sulfated alkyl,
aralkyl, and alkaryl anionic compounds; alkyl succinates; alkyl
sulfosuccinates; N-alkanoyl sarcosinates; and the like. Preferred
are the sodium, magnesium, ammonium, and the mono-, di- and
triethanolamine salts of alkaryl sulfonates. The alkyl groups
preferably contain 8 to 22 carbon atoms. Sulfate ethers are
contemplated, preferably containing 1 to 10 ethylene oxide and/or
propylene oxide units. Preferred examples of anionic surfactants
include sodium lauryl sulfate, sodium lauryl ether sulfate,
ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium
C.sub.14-16 olefin sulfonates, ammonium pareth-25 sulfate, sodium
myristyl ether sulfate, ammonium lauryl ether sulfate, disodium
monooleamido-sulfosuccinate, ammonium lauryl sulfosuccinate, sodium
dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate,
sodium N-lauroyl sarcosinate, and the like.
Examples of amphoteric surfactants with which the copolymers of the
present invention can be formulated include
cocoamphocarboxyglycinate, cocoamphocarboxypropionate, cocobetaine,
N-cocoamidopropyldimethylglycine, and
N-lauryl-N'-carboxymethyl-N'-(2-hydroxyethyl)ethylenediamine, as
well as the betaine and sultaine compounds disclosed in the CTFA
Dictionary as useful in personal care products.
Examples of useful nonionic surfactants with which the copolymers
of the present invention can be formulated include fatty acid mono-
and dialkanolamides in which the fatty portion preferably contains
from about 10 to about 21 carbon atoms, and amine oxides, such as
N-alkyl amine oxides.
A typical shampoo formulation comprises from about 3 to about 30
weight percent of an anionic and/or amphoteric surfactant
component, from about 0.1 to about 10 weight percent of a nonionic
surfactant component, together with from about 0.1 to about 20
weight percent of one or more copolymers of the present invention,
and water. The formulation also preferably comprises an effective
amount, on the order of from about 0.1 to about 5 weight percent,
of a thickener. Examples of suitable thickeners include, for
example, sodium alginate, gum arabic, polyoxyethylene, guar gum,
hydroxypropyl guar gum, cellulosics, such as methyl cellulose,
methylhydroxypropyl cellulose, and hydroxypropylcellulose, starch
derivatives, such as hydroxyethylamylose, locust bean gum,
polysaccharides, and the like.
The advantages and the important features of the present invention
will be more apparent from the following examples.
EXAMPLES
Example 1
Preparation of the Copolymers of the Invention
In a 1L 4-neck flask equipped with a mechanical stirrer, addition
funnel, and reflux condenser, .alpha.,.omega.-hydrogensiloxane
(charges provided in Table 1) of the general formula
HSi(CH.sub.3).sub.2 O{Si(CH.sub.3).sub.2 O}.sub.p
Si(CH.sub.3).sub.2 H was heated to 80.degree. C. A slow addition of
allyl glycidyl ether started at 80.degree. C. after chloroplatinic
acid (5 to 10 ppm as Pt) had been added to the flask. The
temperature was maintained at 80 to 90.degree. C. until no SiH
could be detected. The excess allyl glycidyl ether was removed by
vacuum stripping at 50 mm Hg and 120.degree. C. The resulting epoxy
end-blocked fluid was characterized by its epoxy equivalent
weight.
Charges for the Preparation of the Epoxy End-blocked Polysiloxanes
Allyl Glycidyl Typical Epoxy SiH Charge Ether Charge Designation of
Equivalent "p" (g) (g) the Epoxy Fluid Weight (g) 50 500 31.2 E-I
2127 100 500 15.9 E-II 3703
In a second step, the amine/amines of choice (detailed charges
provided in Table 2), a sufficient amount of 2-propanol to make a
60 percent solution of the final copolymer, and 100 ppm of Vitamin
E, were placed in a 1 L four-neck flask equipped with a stirrer,
addition funnel, reflux condenser, and thermometer. The temperature
of the reaction mixture was adjusted to 80.degree. C. and
.alpha.,.omega.-diepoxysiloxane and diepoxy- polyalkyleneoxide were
added from the addition funnel, either at once or in two portions,
allowing two hours between additions. After the reaction was
complete (epoxy functionality was consumed), solvent was removed by
distillation and the resulting fluid was used as is or after
neutralization with acetic acid.
TABLE 2 Charges for the Preparation of the Copolymers Copoly-
Copoly- Copoly- Copoly- Copoly- mer I mer II mer III mer IV mer V
Epoxy- E-II E-I E-II E-I E-I silicone Charge of 701.6 400 140.2
159.6 160.0 the Epoxy- silicone (g) Epoxy- DER 732 DER 732 DER 732
DER 732 DER 732 polyalky- lene-oxide Epoxy- 70.4 52.4 28.2 25.3
24.5 polyalky- lene-oxide charge (g) Ethanol- 13.1 11.2 4.4 4.8 5.4
amine charge (g) Diethanol- 3.0 3.6 -- -- -- amine charge (g) Molar
10% 22% 10% 5% 18% Excess of Amine Appearance Milky Hazy Hazy Clear
Clear of the product Viscosity 12,600 12,800 >50,000 >50,000
26,700 (cps)
Example 2
Testing Softening Properties of (AB).sub.n A Copolymers
In this example, the test fabric and test procedures used were as
follows: Bleached Cotton Interlock Knit, Style 460 (Test Fabrics
Inc., Middlesex N.J.)
Test Procedures Conditioning Textiles for Testing, ASTM Method
D-1776-79 Absorbency of Bleached Textiles, AATCC Method 79-1992
Softness evaluation was done by a hand panel and the tested fabrics
were rated on a scale of from 1 to 10 (1 being the harshest).
Selected copolymers of the present invention (as dispersions in
water) and MAGNASOFT SRS (control, commercial premium (AB).sub.n
polysiloxane aminopolyalkyleneoxide softener from OSi Specialties,
Greenwich, Conn.) were applied to 100 percent cotton knit fabric
from a pad bath. The softener concentration in the finishing
composition was such that the effective add-on level on the fabric
was 1 percent. Curing conditions were 171.degree. C. for 1.5
minutes. Softening and absorbency data are summarized in Table
3.
TABLE 3 Softness Rating and Wettability Copolymer Softness Wetting
Time (sec) Magnasoft SRS 5.75 >90 Copolymer I 8.0 5.4 Copolymer
II 7.75 2.6 Copolymer III 5.0 5.8 Copolymer IV 5.1 6.1 Copolymer V
7.8 9.5 Untreated Control 1.25 0.2
Table 3 demonstrates that the non-(AB).sub.n A copolymers of the
present invention provide softening properties at least equivalent
to, and wetting properties superior to, MAGNASOFT SRS silicone.
Example 3
Testing Hair Conditioning Properties
In a side-by-side comparison test, human hair was washed with a
control shampoo and a conditioning shampoo containing either
Silsoft A-843, an (AB).sub.n type copolymer or the products of the
present invention.
Hair Testing Procedure
Wet and dry combability are measured as the number of inches a comb
travels when a 10-inch long hair tress, placed on a calibrated
chart, is combed from top to bottom. Fly away is reported as the
difference between the total width of the entire tress and the
width of the hair bundle after the tress is combed quickly 10
times. Combability, appearance, and fly-away data are summarized in
Table 4.
PREPARATION OF SHAMPOO Control Conditioning (Wt %) (Wt %) Ammonium
Lauryl Sulfate, 28% 35.0 35.0 Lauramide DEA 3.0 3.0 PEG-120 Methyl
Glucose Dioleate 2.0 2.0 "Glucamate" DOE-120.sup.a 1.0 Silicone
Conditioning Ingredient Citric Acid, anhydrous 0.4 0.4
Cocamidopropyl Betaine, 35% 10.0 10.0 Dimethicone Copolyol, 2.5 2.5
SILWET .RTM. surfactant L-7657.sup.b Deionized Water qs to 100 qs
to 100 Preservative qs qs .sup.a Amerchol .sup.b OSi Specialties,
Inc. The term "qs" means "quantity sufficient."
Procedure: Water was mixed with ammonium lauryl sulfate. The
solution was heated to 45.degree. C. and the remaining ingredients
were added in the order listed, waiting for each ingredient to
dissolve before adding the next. Preservative was added after
cooling the formulation to room temperature.
TABLE 4 Properties of Hair COMB- COMB- ABILITY ABILITY WET DRY
FLY-AWAY FEEL TREAT-MENT (INCHES) (INCHES) (INCHES) WET/DRY Control
Shampoo 2.7 5.0 10.0 Draggy/dry Conditioning Shampoo with 10 10 3.0
Rich/Very Copolymer I silky soft Conditioning Shampoo with 10 10
2.5 Rich/Very Copolymer II silky soft Conditioning Shampoo with 10
10 3.5 Rich/Very Copolymer III silky soft Conditioning Shampoo with
10 10 3.0 Rich/Very Copolymer IV silky soft Conditioning Shampoo
with 10 10 Rich/Very Copolymer V silky soft Conditioning Shampoo
with 6.5 9.5 3.5 Dry/Silky Silsoft A-843 soft
Hair washed with the conditioning shampoo containing the
conditioning ingredients of the present invention had improved wet
and dry combability and the after feel as compared to Silsoft A-843
silicone copolymer.
In view of the many changes and modifications that can be made
without departing from principles underlying the invention,
reference should be made to the appended claims for an
understanding of the scope of the protection to be afforded the
invention.
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